Precise Synthesis of Poly(N,N-Dimethylacrylamide) by Group Transfer Polymerization Using a Strong Brønsted Acid and an Amino Silyl Enolate

Abstract

This chapter describes the group transfer polymerization (GTP) of N,N-dimethylacrylamide (DMAA) promoted by bis(trifluoromethanesulfonyl)imide (Tf2NH), one of the strong Brønsted acids, which proceeded in a living fashion for the synthesis of polyacrylamides with well-defined structures. The Tf2NH-promoted GTP of DMAA initiated by (Z)-1-(dimethylamino)-1-trimethylsiloxy-1-propene ((Z)-DATP), an amino silyl enolate, at 0 °C homogeneously proceeded to produce PDMAA with a predetermined molecular weight and a narrow molecular weight distribution. The living nature of the polymerization was confirmed by the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis, kinetic measurements, and a post polymerization experiment.